US2022087989A1PendingUtilityA1

Aryl-aniline and heteroaryl-aniline compounds for treatment of skin cancers

54
Assignee: NFLECTION THERAPEUTICS INCPriority: Nov 20, 2018Filed: Nov 20, 2019Published: Mar 24, 2022
Est. expiryNov 20, 2038(~12.4 yrs left)· nominal 20-yr term from priority
A61P 35/00A61K 31/4375A61K 31/4025A61K 31/381A61K 31/4365A61K 31/437A61K 31/44A61K 31/42A61K 31/40A61K 31/337A61K 31/397A61K 31/277A61K 31/422A61K 31/4535
54
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Claims

Abstract

Provided herein are compounds and pharmaceutical compositions thereof for treating a skin cancer in a subject in need thereof, wherein the compound is according to any one of formula (I), (II), (III), (IV), and (V): wherein X 1 , X 2 , X 3 , R 1 , R 2 , R 2a , R 13 , R 13a , R 23 , R 23a , R 23b , R 33 , R 33a , R 33b , R 43 , R 43a , R 51 , R 53 , R 53a , R 53b , bond “a”, and subscript n are described herein.

Claims

exact text as granted — not AI-modified
1 . A method of treating or preventing a skin cancer, the method comprising administering to a subject in need thereof a therapeutically effective amount of a compound selected from the group consisting of formula (I), (II), (III), (IV), and (V): 
       
         
           
           
               
               
           
         
         or a N-oxide, stereoisomer, mixture of stereoisomers, and/or a pharmaceutically acceptable salt thereof, 
         wherein:
 X 1  is —CR 13b or  N; X 2  is C 1 -C 6  alkyl; X 3  is S or O; 
 subscript n is an integer from 0 to 2; 
 bond “a” is a single or double bond; 
 R 1  is —OR 4 , —NR 5 R 5a , —N(OR 5b )R 5a , or a N-linked heterocycloalkyl which is unsubstituted or substituted with one or two R 6 ; 
 R 2  is halo, C 1 -C 6  alkyl, —S—C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 2 -C 6  alkenyl, or C 2 -C 6  alkynyl; 
 R 2a  is halo or C 1 -C 6  alkyl; 
 R 4 , R 5 , and R 5b  are each independently hydrogen, C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 3 -C 8  cycloalkyl-C 1 -C 6  alkyl, C 1 -C 6  hydroxyalkyl, C 1 -C 6  alkoxy-C 1 -C 6  alkyl, amino-C 1 -C 6  alkyl, C 1 -C 6  alkylamino-C 1 -C 6  alkyl, di-(C 1 -C 6  alkyl)amino-C 1 -C 6  alkyl, heterocycloalkyl, heterocycloalkyl-C 1 -C 6  alkyl, or R 7 —C(O)—C 1 -C 6  alkyl, wherein each of the C 3 -C 8  cycloalkyl and heterocycloalkyl groups is unsubstituted or substituted with one to six R 6 ; 
 R 5a  is hydrogen or C 1 -C 6  alkyl; 
 each R 6  is independently halo, hydroxy, oxo, C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 1 -C 6  alkoxy, C 1 -C 6 -hydroxyalkyl, C 1 -C 6  haloalkyl, amino, C 1 -C 6  alkylamino, di-(C 1 -C 6  alkyl)amino, amino-C 1 -C 6  alkyl, C 1 -C 6  alkylamino-C 1 -C 6  alkyl, or di-(C 1 -C 6  alkyl)amino-C 1 -C 6  alkyl; 
 R 7  is hydroxy, C 1 -C 6  alkoxy, amino, C 1 -C 6  alkylamino, di-(C 1 -C 6  alkyl)amino, hydroxyamino, or N—C 1 -C 6  alkyl hydroxyamino; 
 R 13 , R 13a , and R 13b  are each independently hydrogen, halo, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, or C 2 -C 6  alkynyl; 
 R 23 , R 23a , and R 23b  are each independently hydrogen, halo, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  alkoxy, or C 3 -C 8  cycloalkoxy; 
 R 33 , R 33a , and R 33b  are each independently hydrogen, halo, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  alkoxy, or C 3 -C 8  cycloalkoxy; 
 R 43  is cyano, —C(O)NR 48 R 48a , or —C(O)R 46 ; 
 R 43a  is hydrogen, halo, C 1 -C 6  alkyl; or 
 R 43  and R 43a  together form —CH 2 CH 2 C(O)— or —CH 2 CH 2 CH 2 C(O)—, each of which is unsubstituted or substituted with one or two R 49 ; 
 R 46  is hydrogen, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 3 -C 8  cycloalkyl or heterocycloalkyl; 
 R 48  and R 48a  are independently hydrogen or C 1 -C 6  alkyl; and 
 each R 49  is independently C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, or C 3 -C 8  cycloalkyl-C 1 -C 6  alkyl; 
 R 51  is hydrogen, C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 3 -C 8  cycloalkyl-C 1 -C 6  alkyl, C 1 -C 6  hydroxyalkyl, C 1 -C 6  alkoxy-C 1 -C 6  alkyl, amino-C 1 -C 6  alkyl, C 1 -C 6  alkylamino-C 1 -C 6  alkyl, di-(C 1 -C 6  alkyl)amino-C 1 -C 6  alkyl, heterocycloalkyl, heterocycloalkyl-C 1 -C 6  alkyl, R 7 —C(O)—C 1 -C 6  alkyl, or —OR 54 , wherein each of the C 3 -C 8  cycloalkyl and heterocycloalkyl groups is unsubstituted or substituted with one to six R 6 ; 
 each R 53  is independently halo or C 1 -C 6  alkyl; 
 R 53a  and R 53b  are each independently hydrogen, halo, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, or C 2 -C 6  alkynyl; and 
 R 54  is hydrogen, C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 3 -C 8  cycloalkyl-C 1 -C 6  alkyl, C 1 -C 6  hydroxyalkyl, C 1 -C 6  alkoxy-C 1 -C 6  alkyl, amino-C 1 -C 6  alkyl, C 1 -C 6  alkylamino-C 1 -C 6  alkyl, di-(C 1 -C 6  alkyl)amino-C 1 -C 6  alkyl, heterocycloalkyl, heterocycloalkyl-C 1 -C 6  alkyl, or R 7 —C(O)—C 1 -C 6  alkyl, wherein each of the C 3 -C 8  cycloalkyl and heterocycloalkyl groups is unsubstituted or substituted with one to six R 6 . 
 
       
     
     
         2 . The method of  claim 1 , wherein the compound has formula (Ia) or (Ib): 
       
         
           
           
               
               
           
         
       
     
     
         3 - 8 . (canceled) 
     
     
         9 . The method of  claim 1 , wherein X 2  of formula (II) is C 1 -C 3  alkyl. 
     
     
         10 . The method of  claim 1 , wherein X 2  is methyl. 
     
     
         11 . The method of  claim 1 , wherein R 23 , R 23a , and R 23b  are each independently hydrogen, halo, C 1 -C 6  alkyl, or C 1 -C 6  alkoxy. 
     
     
         12 . The method of  claim 1 , wherein R 23  and R 23b  are each hydrogen and R 23a  is halo, C 1 -C 6  alkyl, or C 1 -C 6  alkoxy. 
     
     
         13 . The method of  claim 1 , wherein R 23  and R 23b  are each hydrogen and R 23a  is fluoro, methyl, or methoxy. 
     
     
         14 . The method of  claim 1 , wherein R 23 , R 23a , and R 23b  are each hydrogen. 
     
     
         15 . The method of  claim 1 , wherein the compound has formula (IIIa) or (IIIb): 
       
         
           
           
               
               
           
         
       
     
     
         16 - 21 . (canceled) 
     
     
         22 . The method of  claim 1 , wherein the compound has the formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         23 - 37 . (canceled) 
     
     
         38 . The method of  claim 1 , wherein R 1  is —NR 5 R 5a  and R 5  is —OR 5b . 
     
     
         39 . The method of  claim 1 , wherein R 1  is —N(OR 5b )R 5a ; R 5b  is hydrogen, C 1 -C 6  alkyl, C 3 -C 8  cycloalkyl, C 3 -C 8  cycloalkyl-C 1 -C 6  alkyl, C 1 -C 6  hydroxyalkyl, C 1 -C 6  alkoxy-C 1 -C 6  alkyl, amino-C 1 -C 6  alkyl, C 1 -C 6  alkylamino-C 1 -C 6  alkyl, di-(C 1 -C 6  alkyl)amino-C 1 -C 6  alkyl, heterocycloalkyl, heterocycloalkyl-C 1 -C 6  alkyl, or R 7 —C(O)—C 1 -C 6  alkyl; R 7  is hydroxy, C 1 -C 6  alkoxy, amino, or hydroxyamino; and each of the C 3 -C 8  cycloalkyl and heterocycloalkyl groups is unsubstituted or substituted with one to six R 6  and each R 6  is independently hydroxy or C 1 -C 6  alkyl. 
     
     
         40 . The method of  claim 1 , wherein —OR 5b  is selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         41 . The method of  claim 1 , wherein R 1  is —NR 5 R 5a  or —N(OR 5b )R 5a , and R 5a  is hydrogen. 
     
     
         42 - 45 . (canceled) 
     
     
         46 . The method of  claim 1 , wherein the compound has formula (Va) or (Vb): 
       
         
           
           
               
               
           
         
       
     
     
         47 - 56 . (canceled) 
     
     
         57 . The method of  claim 1 , wherein R 2  is halo, C 1 -C 6  alkyl, —S—C 1 -C 6  alkyl, or C 2 -C 6  alkynyl. 
     
     
         58 . The method of  claim 1 , wherein R 2  is halo. 
     
     
         59 . The method of  claim 1 , wherein R 2  is iodo. 
     
     
         60 - 61 . (canceled) 
     
     
         62 . The method of  claim 1 , wherein R 2  is —S—C 1 -C 6  alkyl. 
     
     
         63 . The method of  claim 1 , wherein R 2  is —SCH 3 . 
     
     
         64 . The method of  claim 1 , wherein R 2  is C 2 -C 6  alkynyl. 
     
     
         65 . The method of  claim 1 , wherein R 2  is acetylenyl. 
     
     
         66 . The method of  claim 1 , wherein R 2a  is halo. 
     
     
         67 . The method of  claim 1 , wherein R 2a  is fluoro. 
     
     
         68 . The method of  claim 1 , wherein R 2a  is C 1 -C 6  alkyl. 
     
     
         69 . The method of  claim 1 , where R 2a  is methyl. 
     
     
         70 . The method of  claim 1 , wherein the compound is selected from the group consisting of Compounds in Tables 1 to 5. 
     
     
         71 . The method of  claim 1 , wherein the compound is administered with a pharmaceutically acceptable carrier in a pharmaceutical composition. 
     
     
         72 . The method of  claim 1 , wherein the skin cancer is a cutaneous squamous-cell carcinoma. 
     
     
         73 . The method of  claim 1 , wherein the skin cancer is a MEK-inhibitor responsive or MEK-mediated cutaneous squamous-cell carcinoma. 
     
     
         74 . The method of  claim 1 , wherein the cutaneous squamous-cell carcinoma is associated with activation of p-ERK. 
     
     
         75 . The method of  claim 1 , wherein the compound having any one of formulae (I) to (V) or the pharmaceutical composition thereof is administered topically, subcutaneously, intradermally, or intralesionally. 
     
     
         76 . The method of  claim 1 , wherein the compound having any one of formulae (I) to (V) or the pharmaceutical composition thereof is administered as a lotion, a spray, an ointment, a cream, a gel, a paste, and a patch.

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